Preparing chemical products from olefines and olefine-containing mixtures



Fe'b'. 12, 1924.

A. S. RAMAGE PREPARING CHEMICAL PRODUCTS FROM OLEFINES AND OLEFINE CONTAINING MIXTURES Filed March v,

attenuato Panarea Feb. 12, 1924.

UNITED STATES PATeNToFFlcE.

ALEXANDER S. RAMAGE, OF DETROIT, MICHIGAN, ASSIGNOR TO IBOSTAPH ENGINEER- ING CORPORATION, OF DETROIT, MICHIGAN, Ay CORPORATION OF NEW YORK.

vPIBEIIPARING' CHEMICAL PRODUCTS FROM OLEFINES AND OLEFINE-CONTAINING MIXTUBES.

` Application led March 7, 1918. Serial No. 221,015.

To all/'whom t may concern:

Be it known that I, ALEXANDER S. RAM- AGE, a citizen of the United States, residing at Detroit, in the county of Wayne and C State of Michigan, have invented certain new and-useful Improvements in Preparing Chemical Products vfrom Olenes and Olene-Containing Mixtures, of which the following is a specification. This invention is a process of pre aring chemical products, inc uding nitroerivatives, from olefines and mixtures thereof with aromatic hydrocarbons (benzol, toluol, xylol, etc). The process will be particu- 1li larly described by reference to its application to such hydrocarbon mixtures, including mixtures of olene and aromatic hydrocarbons, as may be produced in the practice of the process descrlbed in my prior Patent 1,224,7 87 patented May 1, 1917. The invention is not, however, restricted to the treatment of hydrocarbon mixtures prepared in this particular manner, but is applicable generally to h drocarbon mixtures rich in olefines, whet er produced by the cracking or catalytic decomposition of mineral oils, or

' otherwise.r

The following is a'speciiic illustrative lexample of my process as applied to a hydro-v carbon mixture containing components vboiling between 20 and 150 C., and'consisting of 'olenes and aromatic bodies in approximately equal proportions. My invention is not restricted, however, to the particular :operating conditions and manipulations below described, nor to the performance of all of thesteps involved in the production and recovery of the products formed. f AThe accompanying drawing is a flow sheet 40 graphically indicating the essential steps of the preferred process as described below. l To a condensate of the character men- I tioned above I add about Y20% by volume 'v ofV 66 sulfuric acid, the acid being introduced very slowly with agitation yand cooling, the tem below 40 The agitatlon is pre erably continued for about ten minutes after the last of the acid has been added, in order to A complete thel reaction. Upon settling the mixture two layers are formed, viz. (1) .an

- acid sludge; and (2) a supernatant mixl A ,ture of quid hydrocarbons, referred to as the hereinafter 01'17.

erature being preferabl held' y The acid sludge consists essentially of: (a) Acid sulfate derivatives of the lighter olenes, chlely those up to and including 10 20' i f (b) Acid resins derived chiefly from the higher olenes.

I add to the acid sludge an approximately equal Volume of water, agitate for about ten minutes, and allowl to stratify. Thereby I obtain a lower aqueous solution containing the alcohols derived from the acid sulfates by hydrolysis; this solution isdistilled and the alcohols recovered. The upper layer is tarry/in appearance and contams the acid resins; These are dissolved 1 n dilute (say 10%) caustic soda, using Just suiicient alkali to produce the soluble resin soaps. By addition of acid the acid resins are re-precipitated from these soa s 1u pui-died form. The resin is soluble 1n ether, alcohols and in solventna htha, but is substantially insoluble in para n hydrocarbons.

v'The oil formedl by theoriginal sulfuric- V A' sample of the oil is tested with 10% by volume of 66 sulfuric acid in order to make sure that suicient acid was em loyed in the original treatment; under thls test the acid should not be colored beyond a In this connection it is light straw color. pointed out that the bodies referred to above as polymerized oleines are not further acted upon by sulfuric acid under the conditions of the original treatment.

- 1 upto1oo f The oil is now fractionated, taking the' following fractions:

and observing the usual precautions for making mono-nitro-benzol'. For example, for each 100 kilograms of hydrocarbon I may use 300 kilograms of nitrating acid consisting of 180 kilograms of 66 sulfuric acid and 120 kilograms of nitric acid of specific gravity 1.42. At the conclustion of the reaction the mixture is permitted to settle and the spent acid run oil". The-crude nitrated product comprises nitro-benzol and nitro-derivatives of the olenes. These latter bodies are readily soluble in dilute caustic alkali, and I separate them by treating the mixture with an excess of dilute (5-10%) caustic soda,

which leaves the nitro-benzene substantially ure.

p Fraction No. 2 is treated in an identical manner, the alkaline treatment leaving practically pure nitro-toluol, which is substantially pure mono-nitro-toluol, in case the operation has been carried out With the production of this body in view.

The'alkaline solutions of the nitro-derivatives of the olefines prepared in the course of the above operations may be neutralized With acid, yielding a solid precipitate, which may be further purified by Washing with Water. Further nitration of this precipitate yields a crystallizable nitro-body. Both of the above nitro-bodies are soluble in cold alcohol.

Fraction No. 3 consists of xylol and olene bodies, and is treated in the same manner as fractions Nos. 1 and 2, yieldin nitroxylol and nitro-derivatives of the ole es.

Fraction No. 4 is com'posed esentially of olene bodies up to CMHSO. The effect of the distillation to which this fraction has been subjected is such that these oleine bodies are again susceptible of polymerization under the action of 66 sulfuric acid;l

and they are preferably so polymerized, whereby products of still higher boiling oint are obtained. The treatment of this raction with sulfuric acid, including the formation and separation of an acid sludge, is substantially as already described inconnection with the original distillate, except that the acid sludge consists practically entirely of acid resins, being substantially free from hydrolyzable acid derivatives. The operation of polymerizing the olefines and distilling the polymerized products may be repeated if desired one or. more times in order to convert ractically the Whole of the material into hig -boiling products suitable rfor lubricatin purposes.

Fractions os. 5 and 6 may be used directly for lubricating pur oses, and are characterized by a hlgh lu ricating value and extremely low freezing point, being capable of withstanding the ice-salt test. Or these fractions may serve as the basis for the production of various chemical bodies by synthetic methods.

In case olefines only are present in the original hydrocarbon mixture (absence'of aroniatics) the mani ulative features of the process in so far as t e polymerization of the olefines and the production of the acid sludge are concerned, remain essentially 'as hereinabove described, the proportion of sulfuric acid used bein sufficient for complete transformation of t e olefines, that is to say, suficient to yield a product which u on further testingl With sulfuric acid of ike concentration exhibits little or no evidence of further action. Nitration of the fractions need not of course Abe practiced in this case except as nitro-derivatives of the olefines are desired. The polymerized oleiines may be fractionated as above described to isolate the higher-boiling products; and the lower-boiling fractions may be subjected again to the polymerizing treatment, precisely as above described.

The statement in certain claims that the sulfuric acid is used in proportion sufficient to transform the olefines has reference to both types of transformation herein mentioned, that is to say, the polymerization and the formation of hydrolyzable sulfuric acid derivatives. In so far as acids other than sulfuric acid may effect the polymerization of the olefines, such acids are to be regarded as equivalent to sulfuric acid for the urposes of this invention. Strong hydroc loric acid for example is capable of bringing about a like polymerization.

This application is a continuation, in part of my copending application Serial Number 160,224, filed April 6, 1917.

1. The process of treating hydrocarbon oils consisting essentially of olefine and aromatic hydrocarbons, consisting in reactin thereon with sulfuric acid in proportion sucient to transform substantially all of the olefines, into polymerized products and hydrolyzable sulfuric acidderivatives separatin the treated oil from the acid sludge, and ractionally distilling the aromatic hydrocarbons from the higher-boiling polymerized olefines.

' 2. In a process of preparing high-boiling olefines from low-boiling olefines, the steps which consist in treating a hydrocarbon oil containing low-boiling olefines with sulfuric acid in proportion suicient to effect a substantially complete transformation of the olenes', into olymerized products and hydrolyzable su furic acid derivatives separting the treated oil from the acid sludge, and fractionally distilling the remaining lowboiling hydrocarbons from the high-boiling polymerized olefines.

l3. In a process of'preparing high-boiling olenes from low-boiling oleines the steps which consist in treatin a hydrocarbon oil containing low-boiling o efines with sulfuric acid in proportion sufcient to effect a substantially complete transformation of the oleines, into polymerized products and hy drolyzable sulfuric acid derivatives separat- 5 ing the treated oil from the acid sludge, separating olenes boiling at about 45"-300o C., by fractional distillation, and further polymerizing the same.

4. The process of treating hydrocarbon oils 10 containing olefines and aromatic bodies, which consists in reacting thereon with strong sulfuric acid in proportion suicient to transform substantially all of the oleine's, into polymerized products and hydrolyzable sulfuric acid derivatives withdrawing the resulting acid sludge, and fractionally separating the aromatic bodies from the highboiling bodies resulting from the polymerization of the olefines.

In testimony whereof, I ax my signature.

ALEXANDER s. RAMAGE. 

